DE2019149A1 - Polymer, process for the production of the same and coating agent - Google Patents

Description

DFL-ING. WALTER ABITZ 2019 149 _i ^WnGhep ' ^{2 ±} April 19 7th Q DR. DIETER F. MORF ¹ ^ "'"''"' DR. HANS-A. BROWN

Postal address 8 München 86, Postfach 860109

Patent attorneys Pienzenauerstraße 28

Telephone 483225 and 486415 Telegrams: Chemindus Munich

FJD- 1297

EI DU PONT DE EEMOURS AND COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A.

Polymer, process for making the same

and coating agents

The invention relates to new polymers, a method for Production of the same and obtained from the new polymers Coating agents. A particular feature of the invention relates to pigmented polymer coating agents, which are in primarily for repainting private vehicles and trucks, Airplanes and the like are suitable.

Conventional alkyd resins of drying oils are known from U.S. Patents 2,530,315, 2,530,316 and 2,964,483. Synthetic drying oils for coating agents can be prepared according to US Pat. No. 2,819,302, and acrylic resins are converted into coating agents by mixing and interpolymerization according to US Pat. Nos. 2 940 950 and 2 940 872. Oxazoline-based drying oils are manufactured for coating agents according to US Pat. No. 3 248 397. However, none of these coating agents give a lacquer suitable for repainting which has the combination of properties desired in today's technology

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Adhesion to the base that has a pigmented primer, uncoated steel, a thermosetting varnish or an acrylic or nitrocellulose varnish. The paint intended for repainting must also be done relatively quickly air dry to form a high gloss without regrinding or polishing, it must have a good gloss easy to recoat and touch up, and excellent weather resistance and durability exhibit. Repainting coating agents made from the new polymer according to the invention have these properties and therefore represent high quality paints for repainting.

The new polymer according to the invention has a structure of a polymerized ethylene-unsaturated monomer containing Polymerized vinyl oxazoline ester units of the general formula

H ₂ C

and has amino ester side groups of the general formula attached to its skeleton

0 R ⁶
-CORN-R '

on what

R is a hydrocarbon group with 2 to 20 carbon atoms, 2

R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ^? and R hydrogen atoms, alkyl groups having 1 to 4 carbon atoms and / or radicals of the composition

ti ο

-CH ₂ -OOR ⁰ - 2 -

009843/1838

can mean

Ir is an aliphatic hydrocarbon group with 1 to 6 carbon atoms,

R and R 'are hydrogen atoms and / or saturated aliphatic Hydrocarbon groups with 1 to 6 carbon atoms can mean while

R is a hydrocarbon group having 3 to 21 carbon atoms means.

Leave from the vinyl oxazoline polymers according to the invention produce coating agents that dry quickly in the air and are excellent on substrates such as primed or unprimed Steel, alkyd paints, alkyd melamine paints, acrylic paints and the like.

The new polymers preferably have a relative viscosity of about 1.03 to 1.30, in particular from about 1.05 to 1.20. The “relative viscosity” is the value that is obtained if the outflow time of the polymer solution is divided by the outflow time of the solvent. The outflow times. are determined according to ASTM test standard D-445-46-T ¹ , method B. A solution of 0.25 g of polymer in 50 cm of ethylene dichloride is used as the polymer solution. The outflow times are determined at 25 ° C with the Ostwald viscometer.

The framework of the new Vinyloxazolinpolymerisate can be from any Types of units of copolymerizable, ethylene-unsaturated monomers exist. Typical monomers for the polymer framework are e.g. vinyl chloride, vinylidene chloride, olefins such as ethylene, propylene and the like, vinyl acetate, dienes with conjugated double bonds and 4 to 10 carbon atoms, such as butadiene, aromatic hydrocarbons with vinylidene groups, such as styrene, alkyl-substituted styrene, such as oc-MethyIstyröl, maleic acid alkyl ester, such as maleic acid dibutyl ester, Vinylpyrrolidone, acrylic acid derivatives, such as acrylonitrile and esters of acrylic acid and methacrylic acid, such as methyl methacrylate, ethyl methaorylate, propyl methaorylate

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eater, butyl methacrylate, hexyl methacrylate., Cyclohexyl methacrylate, 2-ethylhexyl methacrylate and the like, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate and the like, or mixtures of the above-mentioned monomers. A preferred group of monomers are methacrylic acid or acrylic acid alkyl esters with 1 to 8 carbon atoms in the alkyl group, since these polymers form a product of particularly good quality. The polymer structure can also contain a small amount of units of ethylene-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid or maleic acid.

Combinations of monomers that form the framework are particularly valuable of the yinyloxazoline polymers according to the invention and Result in polymers of high quality, such as styrene, Methyl methacrylate, 2-ethylhexyl methacrylate, Cyclohexyl methacrylate, butyl methacrylate, ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate, Acrylonitrile and mixtures thereof.

The proportion of amino ester groups in the new vinyl oxazoline polymers according to the invention is about 0.5 to 15 percent by weight of the polymer. These groups are derived from aminoalkyl esters of acrylic acid or methacrylic acid of the general formula

OR ⁶

CH ₉ = CCO- RN-R '

R ⁹ from, in the

R is an aliphatic hydrocarbon group having 1 to 6 carbons

substance atoms,

6 7

R and R hydrogen atoms or aliphatic saturated carbon hydrogen groups with 1 to 6 carbon atoms and

R ^ represent a hydrogen atom or a methyl group.

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Typical aminoalkyl esters of acrylic or methacrylic acid, the for the preparation of the new polymers according to the invention can be used are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, Methylethylaminoethyl methacrylate, butylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, Methacrylic acid diethylaminopropyl ester, methacrylic acid diethylaminobutyl ester, methacrylic acid diethylaminopentyl ester and diethylaminohexyl methacrylate. Methacrylic acid diethylaminoethyl ester and methacrylic acid are preferred tert-butylaminoethyl ester, since these compounds give a product of particularly good quality and light are available.

The content of oxazoline ester units in the new polymers is about 3 to 35 percent by weight of the polymer. These Units are polymerized into the polymer structure and are derived from monomers of the general formula

R ¹ E ² '.

ι r

Q ... QT ^

H ₉ G - G - R ^3
c 'i

from, in the

R is a hydrocarbon group with 2 to 21 carbon atoms, R is a hydrogen atom or an alkyl group with 1 to 4 carbon - carbon atoms,

E and R hydrogen atoms, alkyl groups with 1 to 4t carbon atoms or residues of the composition

o ■ '■■■■'

"8 - CH ₂ - 0 - C - R

can mean while

R is a Kohlenwasaeratoffgruppe with 2 to 20 carbon atoms means.

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1 row
Preferably R and R are unsaturated aliphatic carbons

Hydrogen groups of fatty acids of drying oils and R is a hydrogen atom. Preferred fatty acids of drying oils, the Can be used to prepare the above oxazoline esters are linseed oil fatty acids, tall oil fatty acids and dehydrated Castor oil fatty acids.

These oxazoline esters can be made according to U.S. Patent 3,248,397. A preferred combination of these Art is the reaction product of 1 mole of tris (hydroxymethyl) aminomethane and 3 moles of tall oil fatty acids, which has then been reacted with formaldehyde. This connection becomes the Time marketed under the name "Chemacoil TA 100". Another preferred compound is, as described above, only with linseed oil fatty acids instead of tall oil fatty acids, manufactured.

The process for preparing the new polymers according to the invention consists in mixing about 3 to 35 percent by weight of vinyl oxazoline ester, 0.5 to 15 percent by weight of acrylic or methacrylic acid aminoalkyl ester and about 50 to 96.5 percent by weight of copolymerizable, ethylene-unsaturated monomers with one another in a suitable solvent mixes. This mixture is then heated to about 50 to 200 ° C. for 1 to 6 hours * until a polymer with a relative viscosity in the above range of 1.03 to 1.30 has formed.

Suitable solvents for the process, which can also be used at the same time to dilute the polymer to form a varnish, are acetone, methyl ethyl ketone, amyl alcohol, ethylene glycol monoethyl ether acetate, ethyl acetate, ethyl alcohol, isopropanol, ethylene dichloride, diacetone alcohol, di-isobutyl-butyl-ketone, acetate, mineral oil, di-isobutyl-butyl-ketone, acetate, mineral oil, di-isobutyl-butyl-ketone-acetate, petroleum-ethyl-ketone oil, methyl-ethyl-ketone-oil, di-isobutyl-ketone-oil , Toluene, xylene, substituted benzenes, benzene, substituted toluenes, hexane, aromatic hydrocarbons, high-boiling petroleum fuels, petroleum hydrocarbons from high

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Solvent power, diethyl ether, methylamyl acetate and butanol. Suitable coating agents consist of about 95 "to 40 percent by weight from one of the organic solvents mentioned above about 5 to 60 percent by weight of the film-forming polymer.

Preferred polymerization catalysts used for the preparation of the new vinyl oxazoline polymers according to the invention are azo catalysts such as azo-bis-isobutyronitrile and the like. The catalyst is preferred in amounts of about 0.01 to 2 percent by weight, based on the amount of monomers. ,

They preferably contain those from the new vinyl oxazoline polymers Vinyloxazoline polymers prepared according to the invention in amounts of about 1 to 95 percent by weight coating and an alkyd resin in amounts from 99 to 5 percent by weight; in particular, the proportion of the new vinyl oxazoline polymers in the coating agent is 50 to 65 percent by weight and the proportion of alkyd or acrylic resin accordingly 50 to percent by weight.

The alkyd resin that can be used to produce the coating agent has an acid number of about 2 to 25 », preferably about to 14, and is about 5 to 7 acid number units from its gel point.

Typical alkyd resins of this type are made from esterification products a fatty acid of a drying oil such as linseed oil, tallol or dehydrated castor oil fatty acid, a polyvalent one Alcohol, a dicarboxylic acid and an aromatic monocarboxylic acid.

Typical polyhydric alcohols for the preparation of the alkyd resins are glycerol, pentaerythritol, trimethylolethane, trimethylolpropane, glycols such as ethylene glycol, propylene glycol, butanediol or pentanediol.

Typical dicarboxylic acids or anhydrides of the same, which are used to produce

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Position of the alkyd resins that can be used are phthalic acid, Phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid and fumaric acid. Typical aromatic monocarboxylic acids are benzoic acid, p-tert-butylbenzoic acid, phenylacetic acid, triethylbenzoic acid.

A preferred alkyd resin is the reaction product of one Aoryl polymer and an alkyd resin. The alkyd part of the The polymer can be any of the alkyd resins described above, while the acrylic part of the polymer is an ester the acrylic acid or methacrylic acid or acrylonitrile can also contain styrene and a small amount, namely 0.5 to 5 percent by weight, of an ethylene-unsaturated mono- or dicarboxylic acid, such as methacrylic acid, acrylic acid, itaconic acid and the like, contains. The acrylic ester portion of the polymer is made first and at an early stage of the alkyd resin production mixed with the alkyd resin and reacted. The polymer is then prepared using conventional polymerization methods manufactured. A preferred polymer of this type is a copolymer of styrene, methyl methacrylate and Methacrylic acid, the alkyd part of which is made up of linseed oil fatty acid, benzoic acid, Pentaerythritol and phthalic anhydride is made.

Any acrylic resin can be used to produce the new coating compositions according to the invention. Preferably the acrylic resin has a relative viscosity of about 1.02 to 1.06, determined as described above. The acrylic resin can be produced from esters of acrylic or methacrylic acid or acrylonitrile and an aromatic hydrocarbon with an α, ß-unsaturated vinyl bond, such as styrene, or from mixtures of these substances. The acrylic resin can also contain methacrylic acid or acrylic acid hydroxyalkyl ester units, such as acrylic acid hydroxyethyl ester or methacrylic acid hydroxypropyl ester units. The acrylic resin can also contain small amounts of units of α, ß-unsaturated carboxylic acids, such as acrylic acid or methacrylic acid. A preferred acrylic resin is made from styrene, butyl acrylate, hydroxyethyl ester and acrylic acid.

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The new coating compositions are preferably pigmented according to the invention, the ratio of pigment to binder being approximately "1: 1.00 to approximately 75: 100." Binder ¹ denotes the film-forming constituents of the coating compositions. Examples of the wide variety of pigments that can be used in connection with the new coating agents according to the invention are metal oxides, preferably titanium dioxide, zinc oxide and the like, metal hydroxides, metal flakes such as aluminum or bronze flakes, chromates such as lead chromate, sulfides, sulfates , Carbonates, soot, silica, talc, china clay, iron blue, organic red dyes, maroon dyes, organic dyes and varnishes, etc.

The pigments can be incorporated into the coating material by first producing a grinding batch with the alkyd resin or the new polymer according to the invention by conventional grinding with sand ¹ in a ball mill and then mixing this with the film-forming polymers, as described in the following examples is.

Plasticizers can also be added to the new coating agents in amounts of up to 10 percent by weight, based on the weight of the binder. Suitable plasticizers are Phthalsäurebenzylbutylester, dibutyl phthalate, Phosphorsäuretriphenylester, phthalic acid-2-äthylhexylbenzylester, Phthalsäuredicyclohexylester, diallyl phthalate, dibenzyl phthalate, Phthalsäurebutylcyclohexyleoter, mixed benzoic acid and Fettölsäureester of pentaerythritol, poly (propylene adipate) dibenzoate, Diäthylenglykoldibenzoat, Tetrabutylthiodisuccinat, butyl-phthalyl-butylglykolät, acetyl , Dibenzyl sebacate, tricresyl phosphate, toluene ethyl sulfonamide, the di-2-ethylhexyl ester of hexamethylene diphthalate, di (njethylcyclohexyl) phthalate. A preferred plasticizer of this group is benzylbutyl phthalate, since it gives a coating agent with an excellent combination of properties .

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Furthermore, the new coating agents are small amounts of conventional metal-containing desiccants, such as lead naphthenate, manganese naphthenate, cobalt naphthenate, leadallate and the like, added. The new coating agents according to the invention can on a wide variety of substrates, e.g. on metal, wood, glass, plastics and the like, using conventional methods, such as spraying, electrostatic spraying, dipping, painting, flow coating and the like will. These coatings can be air dried or about 15 minutes to 2 hours at a relatively low temperature can be baked in at about 65 to 120 C. The coating obtained is about 25 to 125 μ »preferably 50 to 100 μ, thick, has a good gloss and can, if necessary, be rubbed or polished using conventional methods to ensure smoothness, improve the apparent gloss or both. The new coating agents according to the invention give hard, durable, Scratch-resistant, weather-resistant, glossy coatings that are used for painting private or truck bodies of private or truck bodies, plug vehicles, railroad cars, devices, vending machines, installed outdoors Systems and the like are suitable.

Another special feature of the new coating agents according to the invention is that the coating after application and short-term air drying or stoving again coated or for the purpose of two-tone tinting without lifting off a second colored order can be provided. Therefore, these coatings can easily be touched up and with a second coating coating.

The rapid air drying to a glossy lacquer and the excellent adhesion to substrates are characteristic of the coating compositions according to the invention and make them particularly suitable for repairing and repainting cars and trucks. The new coating agents are also suitable for touching up all types of coated metal substrates, such as metals coated with aoryl varnishes, nitro-cellulose varnishes,

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Älkyd melamine paints and the like are coated.

In the following examples, all quantitative data are based on weight , unless otherwise stated.

Example J_ Production of an acrylic vinyl oxazoline ester ^ polymer

Gewiohtsteile Part 1

Toluene 176.0

Acetone 84.8

Part 2 .

Methyl methacrylate 169.5

Butyl methacrylate 213.2

.Methacrylic acid tert-butylaminoethyl ester 29.1

Vinyloxazoline ester of a linseed oil fatty acid (reaction product of 1 mole of tris (hydroxymethyl) aminomethane and 3 moles of linseed oil fatty acids, subsequently reacted with 1 mole of formaldehyde according to US Pat. No. 3,248,397). · ■ '.. 72.6 ^l

■ Azo-bis-isobutyronitrile 3.6

part 3

Azo-bis-isobutyronitrile .1,2

Part 4

Azo-bis-isobutyronitrile 1,2

Part 5

Azo-bis-isobutyronitrile 1,2

part 6th

Toluene 62.0

Total 814.4

Part 1 was heated in a flask equipped with reflux condenser, the reaction vessel at 70 bie 75 ° C. Part 2 is premixed and slowly and continuously added over the course of 2 hours at a constant rate, the reaction

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tion mixture is kept at its reflux temperature, which varies in the range of 70 Ms 82 ° C. The reaction mixture is kept at reflux stone temperature for 1 hour, then with part. added and heated to reflux temperature for another hour.

Part 4 is then added and the mixture is again heated to reflux temperature for one hour. After adding part 5, the mixture is heated in the reflux condenser for 2 hours or until the polymer solids content of the solution has reached at least 63 μl . Then heating the reaction vessel is stopped and part 6 is added.

The polymer solution obtained in this way has a Gardner-Holdt viscosity from X-Z, determined at 25 ° C, and a pesticide content from 58 #.

The polymer is the reaction product of

Weight percent

Methacrylic acid methyl ester. 35

Butyl methacrylate 44

Methacrylic acid tert-butylaminoethyl ester 6

Vinyloxazoline ester of linseed oil fatty acid 15

A total of 100

The polymer solution is applied to a steel plate treated with zinc phosphate and allowed to dry for 1 hour. Of the clear coating has excellent appearance and is smooth, tough and durable.

An alkyd resin is made from the following components:

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JQ parts by weight

Part 1

Linseed oil fatty acids 178.6

Benzoic acid 59.8

Pentaerythritol 123.0

Phthalic anhydride 63.3

Dibutyl tin oxide 0.6

Xylene 21.3

Part 2

Phthalic anhydride 68.7

Xylene 2.8

part 3

Xylene 350.5

Total 869.4 '

The components of part 1 are premixed and placed in a reaction vessel equipped with a reflux condenser on the reflux · heated to a temperature of 166 ° C. The reaction mixture is on maintained at the reflux temperature, which can rise to about 218 C. From time to time the reaction mixture is sampled taken to determine the acid number. When the acid number Reached about 5 to 10, add part 2 and heat it up Reaction mixture back to reflux temperature, which is about 205 ° C. The reaction is continued until the polymer has reached an acid number of 10 to 12. Then you bet Part 3 too.

The polymer solution thus obtained has a polymer solids content of 55 percent by weight, and the polymer has a Gardner-Holdt viscosity of V-Z, determined at 25 ° C.

The polymer is the esterification product of

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ι " percent by weight

Linseed oil fatty acid pentaerythritol ester 41.6

Pentaerythritol benzoate 15 »0

Pentaerythritol phthalate 39.4

Pentaerythritol 4.0

Total 100.0

Regulation No. 1 for pigment dispersion Parts by weight

! Titanium dioxide (after the sulphate process

manufactured) 630.0

Soia glycerol phthalate alkyd resin solution
(55 fo resin solids, "where that
Alkyd resin made from $ 43 soybean oil, 52 grams of glycerin phthalate, and 5 $ glycerin
is) 158.0

Xylene 212.0

Total 1000.0

The ingredients are premixed and placed in a sand mill Grind particle sizes of 7.5 μ.

A paint is made by mixing the following ingredients manufacturedj

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Parts by weight part 1

Pigment dispersion according to regulation No. 1 (63 io titanium dioxide, dispersed in soybean oil alkyd resin and hydrocarbons) 188.02

Soy glycerol phthalate alkyd resin solution

(55 fo resin solids of the previously

font no. 1 for the pigment dispersion. described alkyd resin) 26.10

Alkyd resin solution prepared as above

(55 Io resin solids) 136.90

Aeryl vinyl oxazoline polymer solution, prepared as described above. (58 % polymer solids) 302.59

Cobalt naphthenate solution (6 $ cobalt "in hydrocarbons) 2.68

Manganese naphthenate solution (6 » Manganese in

Hydrocarbons) 0.28

Leadallate solution (24 ^ lead in hydrocarbons) 2.68

Hydrocarbons (boiling range 189-219 ° 0,

Aniline point -28 ° G). ': .. 34.43

Gasoline (boiling range 100-163 ⁰ G) 79.56

Part 2 '".."' ■

Hydrocarbons (boiling range 150-190 ° C,

Aniline point -28 ° C) 79.12

A total of 852.36 part 1 is mixed for 1 hour, after which part 2 is added.

The above paint is thinned to spray viscosity with aromatic hydrocarbons. A 50 micron thick coating of this coating agent is sprayed onto the following panels: motor vehicle body panels that have been primed with a pigmented alkyd primer; steel plates coated with acrylic varnish; steel panels coated with pigmented epoxy primer; steel plates coated with thermosetting aoryl paint; steel plates coated with alkyd varnish; Steel plates coated with alkyd melamine lacquer. Several of the panels coated with the thermosetting acrylic varnish, the alkydlaok and the alkyd melamine varnish are made

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processed with the sandblasting blower before applying the coating, while the coating is applied to the remaining panels without prior sandblasting. In all cases the coating is left on for 30 minutes. Air dry and get a tough, lasting film of excellent quality Gloss, Adhesion and Appearance.

Several panels of each row are allowed to air dry for one week and then in four at high humidity aiest periods examined for the formation of jumps. In each Period, the plates are (1) 24 hours of a relative humidity of 100 $ at 38 ° C, (2) 24 hours of a temperature from -23 C and (3) exposed to room temperature for 4 hours. After each test period, the plates are checked with the magnifying glass examined for leaps and bounds. At the end of the entire test, the panels did not show any cracks in the paint, none Becoming matt and no reduction in the adhesion to the surface.

Several panels of each group are exposed to solar radiation at a 45 ° angle in Florida and gradually and 8 months examined. After 8 months of weathering, all panels have retained their color and are showing excellent gloss, very little chalking and acceptance of water stains and no reduction in the adhesion of the Varnish on the base.

The above tests show that the new coating composition according to the invention provides excellent coatings on metals and adheres well to all types of substrates, even under strict test conditions.

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Example 2

An acrylic vinyl oxazoline ester polymer is made up of the following Components manufactured:

Parts by weight part 1

Toluene 176.0

Acetone 84.8

Part 2 '·.

Methyl methacrylate x 169.5

Butyl methacrylate 213 »2

Dimethylaminoethyl methacrylate 29 »1

Vinyloxazoline esters of tall oil fatty acids (prepared according to Example 1, but with tall oil fatty acids instead of linseed oil fatty acids) 72.6

Azo-bis-isobutyronitrile 3 »6

part 3

Azo-bis-isobutyronitrile 1,2

Part 4 ■■■■. /.-... ·

Azo-bis-isobutyronitrile 1,2

part 5

Azo-bis-isobutyronitrile 1,2

Part 6 .

Toluene 62.0

A total of 814 »4

Part 1 is heated to 70 to 75 ° C in a reaction vessel equipped with a reflux condenser. Part 2 is premixed and slowly added to the reaction vessel over the course of 2 hours at a steady rate and continuously, the reaction mixture being kept at its reflux temperature, which fluctuates from 70 to 82.degree. The reaction mixture is kept at reflux temperature for 1 hour, after which part 3 is added and the reaction mixture again

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Maintains at reflux temperature for 1 hour. After adding part 4, the reaction mixture is heated to reflux temperature for a further hour; then sets one part to 5 and the reaction mixture heated 2 hours or as long reach the Gesamtpolymerisatgehalt the solution at least 63 i ", at reflux temperature. The heating is then interrupted and part 6 is added.

The polymer solution obtained in this way has a Gardner-Holdt viscosity vi
from $ 58>

oosity of X-Z, determined at 25 ° 0, and a pesticide content

The polymer is the polymerization product of the following components:

Parts by weight

Ethyl methacrylate 35

Butyl methaorylate 44

Methaorylsäurediethylaminoäthylester 6

Vinyloxazoline esters of tall oil fatty acids 15

A total of 100

The polymer solution is applied to a steel plate treated with zinc phosphate and allowed to dry for 1 hour. Of the clear coating has an excellent appearance and is smooth, tough and durable.

A paint is made by mixing the following ingredients:

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Part 1

Pigment dispersion according to regulation No. 1 (63 i <* titanium dioxide, dispersed in soybean oil alkyd resin and hydrocarbons according to example 1)

Sο i a glycerol phthalate alkyd resin solution. (55 ia solids in hydrocarbons according to example 1)

Alkyd resin solution (55 # solids, manufactured according to example 1)

Acrylic Vinyloxazoline Tall Oil Fatty Acid Ester Solution (58 io solids, prepared as described above)

Cobalt naphthenate solution ( $ 6> cobalt in hydrocarbons)

Manganese naphthenate solution (6 f * Manganese in hydrocarbons)

Leadallate solution (24 # lead in hydrocarbons)

Hydrocarbons (boiling range 189 to 219 ° C, aniline point -28 ° C) '

Gasoline (boiling range 100 to 163 ° 0)

Part 2

Hydrocarbons (boiling range 150 to ^; 190 ° C, aniline point -28 ° C)

All in all .

2019U9

Parts by weight

188.02

26.10 136.90

302.59 2.68 0.28 2.68

34.43 79.56

79.12 846.72

Part 1 is mixed for 1 hour, after which part 2 is added and mixes thoroughly.

The coating agent obtained in this way is mixed with aromatic hydrocarbons diluted to spray viscosity and sprayed onto a series of steel plates which, as described in Example 1, are coated. Then leave to air dry for 30 minutes. The films obtained in this way show in all cases excellent adhesion to the various substrates, high gloss, excellent Appearance, excellent durability and resistance to the occurrence of cracks at high Moisture determined according to those described in Example 1

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Tests and excellent re-coatability.

Example 3

A paint is made by mixing the following ingredients manufactured:

Parts by weight

Pigment dispersion according to regulation no. 1 (as described in example 1; _{63.7 TiO 2} t dispersed in soya oil alkyd resin and hydrocarbons) 28.12

Cobalt naphthenate solution (6 # cobalt in

Hydrocarbons) '0.40

Manganese naphthenate solution (6 / »Manganese in

Hydrocarbons) 0.30

Leadallate solution (24 # lead in

Hydrocarbons) 0.30

Acrylic vinyl oxazoline polymer solution (prepared according to Example 1;
58 Jo polymer solids) 43.15

Aorylpolymerisatlösung (6 fo Polymerisatfeststoffe in hydrocarbons, wherein the polymer of 45 ° i styrene units, 43 ° Acrylsäurebutylestereinlie i, i th, 8 and 4 $ io Acrylsäurehydroxyäthylestereinheiten Acrylsäureeinhei.ten, based on the weight consists,) 3.32

Hydrocarbons (boiling range 150 to

190 ° C; Aniline point 28 ° C) 24.41

Total 100.00

The coating composition obtained in this way is diluted to spray viscosity with aromatic hydrocarbons and sprayed onto the coated steel plates described in Example 1, whereupon the coatings are allowed to air dry for 30 minutes. The films obtained in this way show in all cases excellent adhesion to a wide variety of substrates, Bowie excellent appearance and excellent durability.

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..'.- ·. ■. ■ Be is ρ ie 1 4

Preparation of an aoryl vinyl oxazoline ester polymer.

Parts by weight part 1

Toluene 727

Acetone 350

Part 2

Styrene 1000

Methyl methacrylate 300

Acrylonitrile 280

Methacrylic acid tert-butylamino

ethyl ester 120

Vinyloxazoline esters of linseed oil fatty acids

(according to example 1) 300

Azo-bis-isobutyronitrile 15

part 3

Azo-bis-isobutyronitrile 5

Part 4

Azo-bis-isobutyronitrile ', "5

Part 5

Azo-bis-isobutyronitrile 5

Part 6

Azo-bis-isobutyronitrile 5

Part 7

Toluene 256

Part 8

Azo-bis-isobutyronitrile 5

Part 9

Toluene 304

A total of 3677

Part 1 is heated to 70 to 75.degree. C. in a reaction vessel equipped with a reflux condenser. Part 2 will initially be v, orge

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mixes and then slowly and continuously with more evenly Added rate to Part 1 over 2 hours while maintaining the reaction mixture at reflux temperature will. The reaction mixture is then held at reflux temperature for a further hour, after which part 3 is added. After this the reaction mixture at reflux temperature for a further hour Has been heated, part 4, part 5 and part 6 are added in a similar manner, with one between each Add the reaction mixture to reflux temperature for 1 hour holds. After adding part 7, the reaction mixture is again kept at reflux temperature, and after adding Part θ is heated to reflux temperature for a further 1 1/2 hours. The reaction mixture is then allowed to cool and sets part 9 to.

The polymer solution obtained in this way has a G-ardner-Holdt viscosity of Z 2 ', a polymer solids content of 53> 0 $ and a relative viscosity of 1.166, determined at 25 ° C according to ASTM-D-445-46-T. Method B.

This polymer is the reaction product of

Weight percent

Styrene 50

Acrylonitrile 14

Methyl methacrylate 15

Methaoryl acid tert-butylaminoethyl ester 6

Vinyloxazoline esters of linseed oil fatty acids 15

A total of 100

The polymer solution produced in this way is applied to a zinc phosphate treated steel plate applied and allowed to dry for 1 hour. The clear coat has an excellent appearance and is smooth and durable.

A paint is made from the same components as the paint according to Example 1, m ±% the lower

00 9843/1838

decided that instead of the acrylic vinyl oxazoline polymer solution according to example 1 in this case that according to the above rule Acryl-vinyl-oxazoline polymer solution produced added will.

The coating agent obtained in this way is according to Example 1 on Spray viscosity diluted and sprayed onto steel plates, some of which are coated with a pigmented alkyd resin primer and another part is covered with an alkyd varnish. The panels are allowed to air dry, and inside In some cases, a tough, permanent paint film with excellent adhesion to the substrate, good appearance, good resistance to peeling with adhesive tape and good recoatability.

Example 5 ¹

Production of an acrylic vinyl oxazoline ester polymer. Parts by weight Part 1 · 2280 Toluene '. 680 acetone 1375 Styrene 2970 Butyl methacrylate 330 Methacrylic acid tert-butylaminoethyl ester Vinyloxazolihester of a linseed oil fatty acid 825 (according to example V) 11th Azo-bis-isobutyronitrile Part 2 88 Azo-bis-isobutyronitrile

A total of 8559

Part 1 is premixed and then heated in a reaction vessel equipped with a reflux condenser for 1 hour to the reflux temperature of 95 ° C. Part 2 is divided into eight equal parts , and while the reaction mixture is heated to reflux temperature

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FFD-1297. SlT

door is held, the individual parts are at intervals of added 45 minutes each.

The polymer solution obtained in this way has a moisture content of 63.9 %, a Gardner-Holdt viscosity of Z 1 and a relative viscosity of 1.1, both determined at 25 ° C.

The polymer is the reaction product of

Weight percent

Styrene. 25th

Butyl methacrylate 54

Methacrylic acid tert-butylaminoethyl ester 6

Vinyloxazoline ester of a linseed oil fatty acid 15

A total of 100

The polymer solution produced in this way is applied to a zinc phosphate treated steel plate applied and allowed to dry for 1 hour. The clear coat has an excellent appearance and is smooth and durable.

A coating agent is made from the ingredients given in Example 1 produced with the difference that the acrylic-vinyloxazoline polymer solution prepared according to the above procedure instead of that of Example 1 is used.

The coating agent obtained in this way is, as in Example 1, on Spray viscosity diluted and applied to steel plates that partly primed with a pigmented alkyd resin and partly coated with an alkyd melamine lacquer. The plates are allowed to air dry and in all cases a tough, durable paint film of excellent quality is obtained Adhesion to the base, good appearance, excellent, good shine and good repositionability.

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FFD-1297 95 "'

example

Production of an acrylic vinyl oxazoline ester polymer. Parts by weight Part 1 720.0 toluene 240.0 Isopropanol. 240.0 Ethyl acetate 990.0 Methacrylic acid methyl ester 540.0 Cyclohexyl methacrylate. 90.0. Methacrylic acid tert-butylaminoethyl ester Vinyloxazoline esters of linseed oil fatty acids 180.0 (according to example 1) 3.6 Azo-bis-isobutyronitrile

Part 2

Azo-bis-isobutyronitrile 18.0

part 3

Toluene 600.0

Total 3621.6

Part 1 is premixed and allowed to reflux for 1 hour in a reaction vessel equipped with a reflux condenser heated by 85 ° G. Part 2 is divided into five equal parts, and each of these parts is repeated at intervals of Added to the reaction mixture for 45 minutes, the latter being held at its reflux temperature. Then sets part 3 is added and the reaction mixture is allowed to cool to room temperature.

The resulting polymer solution has a pesticide content of 48.5 #, a Gardner-Holdt viscosity of Y, and the polymer has a relative viscosity of 1.111, both determined at 25 °.

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The polymer is the reaction product of

Weight percent

Methyl methacrylate 55

Cyclohexyl methacrylate. 30th

Methaoryl acid tert-butylaminoethyl ester 5

Vinyloxazoline ester of linseed oil fatty acid 10

A total of 100

The polymer solution obtained in this way is applied to a steel plate treated with zinc phosphate and dried for 1 hour calmly. The clear coat has an excellent appearance and is smooth and durable.

A coating agent is made from the same components as that of Example 1, but with the difference that in this example the one prepared according to the above specification Aoryl-vinyloxazoline polymer solution instead of those of Example 1 is used.

The coating agent obtained in this way is according to Example 1 on Spray viscosity diluted and applied to the following types of steel panels: With a pigmented alkyd resin primed steel plates, steel plates coated with an acrylic varnish, with a pigmented microcellulose primer coated steel plates and coated with an alkyd melamine lacquer Steel plates. The panels are allowed to air dry and in all cases a tough, durable one is obtained Paint film with excellent adhesion to the substrate, good: appearance, excellent gloss, excellent resistance against peeling off with adhesive tape and against peeling off during recoating.

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Example 7
Manufacture of an acrylic vinyl oxazoline ester polymer.

Weight parts

Part 1

Toluene 720.0

Isopropanol 240.0

Ethyl acetate 240.0

Methyl methacrylate 810.0

2-ethylhexyl methacrylate 540.0

Methacrylic acid tert-butylaminoethyl ester 90.0

Vinyloxazoline esters of tall oil fatty acids

(according to example 2) 360.0

Azo-bis-isobutyronitrile. 3.6

Part 2

Azo-bis-isobutyronitrile 18.0 _

Total 3,021.6

Part 1 is premixed and placed in a reflux condenser Reaction vessel to reflux temperature for 1 "hour heated by 85 ° G. Part 2 is divided into six equal parts, and each of these portions is added sequentially to the reaction mixture at 45 minute intervals, the the latter is kept at reflux temperature. "'

The polymer solution obtained in this way has a pesticide content of 58 »6 #, a Gardner-Holdt viscosity of Z 2, and the polymer has a relative viscosity of 1.092, both determined at 25 ° C.

The polymer is the reaction product of

Weight percent

Methacrylic acid methyl ester
2-ethylhexyl methacrylic acid K
Methacrylic acid tert-butylaminoethyl ester
Vinyloxazoline Esters of Tall Oil Fatty Acids'

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The resulting polymer solution is coated with zinc phosphate treated steel plate applied and allowed to dry for 1 hour. The clear coat is excellent in appearance and is smooth and durable.

A coating agent is made from the components described in Example 1 produced with the difference that the acrylic-vinyloxazoline polymer solution prepared according to the above procedure instead of that of Example 1 is used.

This coating agent is sprayed viscosity according to Example 1 thinned and on steel plates primed with a pigmented alkyd resin, coated with a thermosetting acrylic varnish Steel plates, with a pigmented nitrocellulose primer coated steel panels and with an alkyd melamine lacquer coated steel plates applied. The panels are allowed to air dry and in all cases it forms tough, permanent paint film with excellent adhesion on the base and good appearance.

Example 8 Preparation of aoryl resin.

Parts by weight part 1

Xylene 1637

Part 2

Methyl methacrylate 960

Styrene 960

Methacrylic acid 80

Azo-bis-isobutyronitrile 40

tert-butyl perbenzoate 40

part 3

tert-butyl perbenzoate * 7

Part 4

tert-butyl perbenzoate '7'

Inegeeamt 5731

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PFD-1297 . 1 $ '

Part 1 is placed in a reaction vessel equipped with a reflux condenser heated to 135 ° C. Part 2 is premixed and slowly added to the reaction vessel over the course of 2 hours. While maintaining the reflux temperature one sets Part 3 is added and the reaction mixture is heated for about 45 minutes Reflux temperature. Part 4 is then added and the Gemisoh refluxed for another hour.

The polymer solution thus obtained has a pesticide content of 56.6 <fo and a Gardner-Holdt viscosity of 24, and the polymer has a relative viscosity of 1.045.

This acrylic polymer contains the ingredients in the following Quantities:

. Weight percent

Styrene 48

Methyl methacrylate 48

Methacrylic acid 4

All in all . 100

Manufacture of an acrylic alkyd resin

• Parts by weight part 1

Linseed Oil Fatty Acid 586

Benzoic acid 196

Pentaerythritol 407

... acrylic polymer solution

(according to the above regulation;
56.6 $ polymer solids) 909

Phthalic anhydride . 188

Dibutyl tin oxide 2

Part 2 ;

Phthalic Anhydride 244

part 3

Xylene 11

Carryover 2543

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FFD-1297 Z.U I3 l

Weight parts

Carryover 2543

Part 4

Xylene 23

Part 5

Xylene 1509 ""

A total of 4075

Part 1 is premixed and placed in a reflux condenser The reaction vessel is kept at the reflux temperature until all of the water formed during the esterification is present aborted, which takes about 4 hours. Part 2 is then added, followed by part 3, and the reaction mixture is heated nooh 45 minutes at reflux temperature. Part 4 is then slowly added, the reaction mixture being brought to reflux temperature holds. After slowly adding part 5, the reaction mixture is allowed to cool.

The polymer solution thus obtained has a solids content of 55.3 i "and a Gardner-Holdt viscosity of about 2"; the polymer has an acid value of 16th

The following coating agents are produced according to the procedure of Example 1, but with the following differences:

Coating agent No. 1

The acrylic-alkyd resin solution prepared according to the above procedure is used instead of the alkyd resin solution of Example 1.

Coating agent No. 2

The acrylic-vinyloxazoline polymer solution according to Example 2 is used instead of the aoryl-vinyloxazoline polymer solution of Example 1 and the acrylic-alkyd resin solution prepared according to the above procedure is used instead of the alkyd resin solution according to Example 1.

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Coating agent No. 3

Instead of the acrylic-vinyl oxazoline polymer solution of the example .1 becomes that according to example 4 and instead of the alkyd resin solution used in example 1 for the preparation of the coating agent the acrylic-alkyd resin solution prepared according to the above procedure is used.

Coating agent No. 4

Instead of the acrylic-vinyl oxazoline polymer according to Example 1 the acrylic-vinyl oxazoline polymer solution according to Example 5 used, and> those for the production of the coating agent according to The alkyd resin solution used in Example 1 is replaced by the acrylic alkyd resin solution prepared according to the above procedure.

Coating agent No. 5

Instead of the aoryl-vinyloxazoline polymer of Example 1 the acrylic-vinyl oxazoline polymer solution according to Example 6 used, and the alkyd resin solution used in Example 1 for the preparation of the coating agent by the after replaces the acrylic alkyd resin solution prepared above.

Coating agent No. 6

Instead of the acrylic-vinyl oxazoline polymer of Example 1 the acrylic-vinyl oxazoline polymer solution according to Example 7 used, and the alkyd resin solution used in Example 1 for the preparation of the coating agent by the after replaces the acrylic alkyd resin solution prepared above.

Each of the above coating agents is diluted to spray viscosity according to Example 1 and applied separately to steel plates which have been primed with a pigmented alkyd resin. In all cases, letting the paint dry in the air, and it makes one look. tough, durable PiIm with excellent adhesion to the substrate, excellent appearance, good gloss and good recoatability.

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Claims (1)

2019H9 BI. du Pont de Nemours April 21, 1970 and Company FED-1297 Claims 1. Polymer has a framework of polymerizing ethylenically unsaturated Monomers, characterized in that the skeleton polymerized-in oxazoline ester units of the general formula -f R ¹
I.
σ-
Ι I. I.
H ₂ O- ^ N
I. -C— ι ^v
• C -
H . -R ⁵ contains and as side chains amino ester groups of the general Formula· O R ⁶
-CORN-R ' R has a hydrocarbon group of 2 to 20 carbon, whereby a KoI atoms,
ρ
R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ and R ^{4 are} hydrogen atoms, alkyl groups having 1 to 4 carbon atoms and / or radicals of the composition I.
0 0 9 8 4 3/1 8 ^ QpPY FFD-1297 33 ■ 2G19U9 Π β - GH ₂ - O - C - R can mean
R is an aliphatic hydrocarbon group with 1 to 6 carbon atoms, 6 7
R and R hydrogen atoms or saturated aliphatic hydrocarbon groups having 1 to 6 carbon atoms and R is a hydrocarbon group having 3 to 21 carbon atoms mean. 2. Polymer according to claim 1, characterized in that it from 50 to 96.5 percent by weight from polymerized ethylene-unsaturated monomer units, from 3 to 35 percent by weight from polymerized vinyl oxazoline ester units and to 0.5 to 15 percent by weight consists of pendant amino ester groups. . 3. Polymer according to claim 2, characterized in that the structure of acrylic acid or methacrylic acid ester units or from a mixture of acrylic acid or methacrylic acid ester units and units of an aromatic hydrocarbon with α, β unsaturated vinyl bond 3 4
stands, the radicals R and R the meaning 0. H- β - CH ₂ - O ■ - C - R and R is the remainder of a fatty acid of a drying oil means. 4 · polymer according to claim 3, characterized in that ς
R is a saturated aliphatic hydrocarbon group with 6 7 2 to 4 carbon atoms and R and R hydrogen atoms and / or saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms. 5. polymer NaOH Anspruoh 4, characterized in that dae GerÜB-fe from Methaoryleäurealkylestereinheiten with "1 to - 33- 009843/1838 ^2019U9 8 carbon atoms in the alkyl group and R and R are the residues of linseed oil fatty acids. . 6. Polymer according to claim 4i> characterized in that the structure of methacrylic acid methyl ester units and meth- ^v 2 acrylic acid butyl ester units, R is a hydrogen atom, R is an ethylene group, R is a hydrogen atom, R 1 row a tert-butyl radical and R and R the radicals of linseed oil fatty acids mean. 7 · Polymer according to claim 4, characterized in that the structure consists of methyl methacrylate and butyl methacrylate units consists, R is a hydrogen atom, ir (\ Π 1 row R is an ethylene radical, R and R are ethyl groups and R and R mean the residues of tall oil fatty acids. 8. Polymer according to claim 4, characterized in that the structure of methacrylic acid methyl ester units, acrylic P consists of nitrile units and styrene units, R is a hydrogen atom, R is an ethylene group, R is a hydrogen atom, R ^ a tert-butyl group and R. and R the residues of linseed oil fatty acids mean. 9 · Polymer according to claim 4, characterized in that the structure of styrene units and butyl methacrylate 2 5 units, R is a hydrogen atom, R is an ethylene group, R is a hydrogen atom, R is a tert-butyl group and 1 8
R and R represent the residues of linseed oil fatty acids. 10. Polymer according to claim 4, characterized in that the structure of methaoryl acid methyl ester units and methacrylic acidoyclohexyl ester units consists, R a hydrogen atom, "R · ^ an ethylene group, R a hydrogen atom, 7 18 R 'denotes a tert-butyl group and R and R denote the reactants of linseed oil fatty acids ". 11. Polymer naoh claim 4, characterized in that: the structure of methaoryl acid methyl ester units and meth- 009843/1838 _3y 2019H9 2 acrylic acid-2-äthylhexylestereinheiten "consists, R a.Was hydrogen atom, R ^ an ethylene group, Rr a hydrogen 7 ■ atom, R a tert-butylgr Mean linseed oil fatty acids. , ygpp, 7 ■ atom, R a tert-butyl group and R and R the radicals of 12. A process for the preparation of the polymers according to claim 1 to 11, characterized in that (1) (a) a vinyl oxazoline ester of the general formula in amounts of 3 to 35 percent by weight, (b) an acrylic acid aminoalkyl ester of the general formula 0 R ⁶ • μ ■ ·· - ς '7 CH ₉ = G - 0 ~ 0 - R- N - R' »9 R ^ in amounts of 0.5 to 15 percent by weight, (c) copolymerizable ethylene-unsaturated monomers .in amounts of 50 to 96.5 percent by weight and (d) a polymerization catalyst in amounts of from 0.01 to 2 percent by weight mixes with each other and (2) the mixture for about 1 to 6 hours at about 50 to 200 ° C implements, whereby R is a hydrocarbon group with 2 to 20 carbon atoms, R represents a hydrogen atom or an alkyl group with 1 to Carbon atoms, - 35 - 009843/1838 2019U9 FPD-1297 Gf R ^ and R ^4- hydrogen atoms, alkyl groups with 1 "to 4 carbon atoms and / or radicals of the composition MR - CH ₂ - 0 - C - R can mean R ^ is an aliphatic hydrocarbon group of 1 to 6 Carbon atoms, 6 7
R and R are hydrogen atoms and / or saturated aliphatic Hydrocarbon groups with 1 to 6 carbon atoms, R is a hydrocarbon group having 3 to 21 carbon atoms and R ^ denote a hydrogen atom or a methyl radical. 13 · The method according to claim 12, characterized in that the copolymerizable ethylene-unsaturated monomers Acrylic acid esters or mixtures thereof with aromatic hydrocarbons with <x, ß-unsaturated vinyl bond used. 14. The method according to claim 13-, characterized in that one as the acrylic acid ester, a methacrylic acid or acrylic acid alkyl ester with an alkyl group with 1 to θ carbon atoms or acrylonitrile is used. 15. Coating agent that consists of 5 to 60 percent by weight of a polymer mixture and 95 to 40 percent by weight a solvent for the polymer mixture, daduroh characterized in that the polymer mixture (1) 1 to 95 percent by weight of an aoryl vinyloxazoline ester polymer with a relative viscosity of about 1.03 to 1.30, determined at 25 ° C according to ASTM test standard D-445-46-T, method B, which is a Structure of polymerized ethylene-unsaturated monomer units and polymerized vinyl oxazoline ester units of the general formula - 36 - 009843/1838 PKB-1.97 « ^2019U9 with amino ester side groups of the general formula 0 E ⁶ η ς ι γ - C - 0 - R- N - R. R has a hydrocarbon group of 2 "to 20 carbons, whereby a coals; material atoms, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R and R hydrogen atoms, alkyl groups from 1 "to 4f carbon atoms and / or residues of the composition , ■. , 0-
-CH ₂ -OOR ⁰ can mean
5
R is an aliphatic hydrocarbon group with 1 to 6 carbon atoms, 6 7 R and R are hydrogen atoms and / or saturated aliphatic Hydrocarbon groups of 1 to 6 carbon atoms and R is a hydrocarbon group with 5 to 21 carbon atoms,
and (2) 99 to 5 percent by weight of an alkyd resin and / or an acrylic resin. 16. Coating agent according to claim 15, characterized in that it is a pigment at a ratio of pigment to Contains binder from about 1: 100 to about 751100. ' - 37 - ' 00 9843/183 8
COPY PFD-1297 3g. 17 · Coating agent according to claim 16, characterized in that it consists of 50 to 65 percent by weight of the acrylic vinyl oxazoline ester polymer and 50 to 35 percent by weight of an alkyd resin. 18 · Coating agent according to claim 17, characterized in that that the, alkyd resin is the esterification product of a fatty acid of a drying oil, a polyhydric alcohol and an aromatic carboxylic acid. 19 · Coating agent according to claim 17, characterized in that that the alkyd resin is an aoryl alkyd resin. 20. Coating agent according to claim 19, characterized in that the acrylic part of the acrylic alkyd resin essentially from styrene, methacrylic acid methyl ester and methacrylic acid units and the alkyd part is the esterification product of fatty acids of a drying oil, a polyvalent one Alcohol and an aromatic carboxylic acid or its anhydride. 21. Coating agent according to claim 17, characterized in that that the structure of the Vinyloxazolinesterpolymerisats from methacrylic acid alkyl ester units, in which the alkyl group Has 1 to 8 carbon atoms, consists of the radicals 1 8
R and R are derived from fatty acids of drying oils, R is a water ^{atom, R 5} and R are radicals of the composition Il f - CH ₂ - O - C - R ^C 5
R is a saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms and R and R are hydrogen atoms and / or saturated aliphatic hydrocarbon groups. with 1 to 4 carbon atoms, and that the alkyd resin is the esterification product of a fatty acid of a drying oil, a polyhydric alcohol and an aromatic carboxylic acid or its anhydride. - 38 - 009843/1838 _na 2019 Ή 9 PFD-1297 33 22. Coating agent according to claim 22, characterized in that that the structure of the vinyloxazoline polymer from butyl methacrylate and methyl methacrylate units 18 5 "consists, R and H the residues of linseed oil fatty acids, R a Ethylene group, R a hydrogen atom, R 'a terto-butyl radical mean and the alkyd resin is the esterification product of linseed oil fatty acids, benzoic acid, pentaerythritol and phthalic anhydride is. 23. Coating agent according to claim 15, characterized in that that the second resin is an acrylic resin. 24 · Coating agent according to claim 23 »characterized in that the acrylic resin consists of styrene units, acrylic acid alkyl ester units, acrylic acid hydroxyalkyl ester units and units of a cc, ß-unsaturated monocarboxylic acid. - 39 - 0098A3 / 1838